Semiconductor light emitting nanoparticle

ABSTRACT

The present invention relates to a method for preparing a nanosized light emitting semiconductor material.

FIELD OF THE INVENTION

The present invention refers to the area of semiconductors and relatesto new quantum dots with improved quantum yields and reduced trapemission, a process for obtaining them and further applications of thenew semiconductors.

BACKGROUND ART

Quantum dots (QD) are semiconducting particles with diameters in thenanometre range (about 2 to 20 nm), which are so small that the opticaland electronic properties of the crystals change. A special feature ofthe Quantum dots is that they change their colour with the particlediameter. In order to produce, for example, blue QDs, no other materialsare required as for red QDs they only have to be produced with differentparticle sizes and/or different composition. In addition to typicalapplications such as displays, QDs are now also used in many otherareas, such as solar cells or processors.

Quantum dots can fluoresce and convert photons to other wavelengths aswell as emit light. However, their outstanding characteristics areundoubtedly the ability to improve the background lighting in displays.LCD TVs use a white background light and then filter the blue, green andred light to display colours. Blue LEDs with a phosphor layer areusually used for this so-called “backlight”.

The strongest technological advantage of QD backlight over phosphorbased “white LED” backlight is the narrow FWHM (<50 nm) which enableswide colour gamut, e.g. increasing the amount of displayed colours. Somephosphor films can give EQE as high as >90%, comparable to EQE of QDfilms.

The most important semiconductor materials, which are also suitable forthe production of Quantum Dots, include cadmium compounds, especiallyCdS and CdSe. However, the disadvantage is that cadmium is highly toxic.A promising alternative would be InP, but here the quantum yield is notsatisfactory. Therefore, the search is ongoing for specific new ligandsimproving quantum of QDs, particularly by reducing trap emission.

Metallic complexes with phosphonates are widely used as precursorsduring the synthesis of Cd-based semiconductor nanocrystals. Suchprecursors are used to make nanorods since they induce anisotropicgrowth. For example it is described in Nature Materials 10, 765-771(2011) and in Journal of American Chemical Society, 123 (1), p. 183-184,2001 to use the following phosphonates as precursors:Cd-octadecylphosphonate, Cd-hexylphosphonate andCd-tetradecylphosphonate.

Furthermore metallic complexes with phosphonates are used as precursorsfor shell growth providing elements of e.g. ZnS, ZnSe shell upon a CdSecore as reported for example in US 2012/0205598 A1. It should bementioned that the metal phosphonates are used as precursors for ZnS andwere decomposed at elevated temperatures, while metal phosphonates arenot mentioned for surface treatment after the synthesis is complete oras a ligand.

It is also known from the paper J. Phys. Chem. Lett. 2011, 2, 145-152that phosphonate acids are useful as QDs capping ligands. The documents,however, are silent with respect to specific metal complexes of thesecompounds and their ability to passivate traps when bound to the outersurface of a QD.

Therefore it has been the object of the present invention to provide newsemiconductor light emitting materials with improved quantum yields.

DESCRIPTION OF THE INVENTION

A first object of the present invention is directed to a semiconductornano-sized light emitting material comprising or consisting of a core,optionally one or more shell layers and a ligand coated onto the core orthe outermost surface of the shell layers, wherein the ligand is one ormore metal phosphonate and/or derivatives thereof, and wherein the metalphosphonate follows one of the following structures according to formula(I), (II), (III), (IV) and/or (V),

wherein R is selected from the group consisting of alkyl, alkenyl,alkynyl, aryl and alkylaryl and wherein R comprises at least 2 and notmore than 20 carbon atoms, and wherein X is selected from the groupconsisting of hydroxyl, ester and ether.

Surprisingly, it has been observed that deposition of ligands of metalphosphonate type and/or derivatives thereof, which are capable ofreplacing native ligands and coordinating to both positive and negativeatoms in quantum material's surface, passivate the traps on the surfaceof the particles, thus leading to a significant increase of up to 60% inquantum yields, improved QY stability and overcomes the drawbacks of theprior art. The effect can further increased by subsequently illuminatingthese materials.

According to the present invention, the term “semiconductor” means amaterial that has electrical conductivity to a degree between that of aconductor (such as copper) and that of an insulator (such as glass) atroom temperature. Preferably, a semiconductor is a material whoseelectrical conductivity increases with the temperature.

The term “nanosized” means the size in between 0.1 nm and 999 nm,preferably 1 nm to 150 nm, more preferably 3 nm to 50 nm.

Thus, according to the present invention, “semiconducting light emittingnanoparticle” is taken to mean that the light emitting material whichsize is in between 0.1 nm and 999 nm, preferably 1 nm to 150 nm, morepreferably 3 nm to 50 nm, having electrical conductivity to a degreebetween that of a conductor (such as copper) and that of an insulator(such as glass) at room temperature, preferably, a semiconductor is amaterial whose electrical conductivity increases with the temperature,and the size is in between 0.1 nm and 999 nm, preferably 0.5 nm to 150nm, more preferably 1 nm to 50 nm.

According to the present invention, the term “size” means the averagediameter of the longest axis of the semiconducting nanosized lightemitting particles.

The average diameter of the semiconducting nanosized light emittingparticles are calculated based on 100 semiconducting light emittingnanoparticles in a TEM image created by a Tecnai G2 Spirit Twin T-12Transmission Electron Microscope.

In a preferred embodiment of the present invention, the semiconductinglight emitting nanoparticle of the present invention is a quantum sizedmaterial.

According to the present invention, the term “quantum sized” means thesize of the semiconducting material itself without ligands or anothersurface modification, which can show the quantum confinement effect,like described in, for example, ISBN:978-3-662-44822-9.

Generally, it is said that the quantum sized materials can emit tunable,sharp and vivid colored light due to “quantum confinement” effect.

In some embodiments of the invention, the size of the overall structuresof the quantum sized material, is from 1 nm to 50 nm, more preferably,it is from 1 nm to 30 nm, even more preferably, it is from 5 nm to 15nm. According to the present invention, said core of the semiconductinglight emitting nanoparticle can be varied. For example, CdS, CdSe, CdTe,ZnS, ZnSe, ZnSeS, ZnTe, ZnO, GaAs, GaP, GaSb, HgS, HgSe, HgSe, HgTe,InAs, InP, InPS, InPZnS, InPZn, InPZnSe, InCdP, InPCdS, InPCdSe, InGaP,InGaPZn, InSb, AlAs, AlP, AlSb, Cu2S, Cu2Se, CuInS2, CuInSe2,Cu2(ZnSn)S4, Cu2(InGa)S4, TiO2 alloys and a combination of any of thesecan be used. The terms “metal phosphonate” and “metal phosphonates” asused herein are interchangeable and include any phosphonate and/orderivatives thereof with a metal cation. Examples of suitable metalcations are listed below.

A second object of the present invention is directed to a semiconductornano-sized light emitting material comprising or consisting of a core,optionally one or more shell layers and a ligand coated onto the core orthe outermost surface of the shell layers, obtainable or obtained by thefollowing steps:

(a) providing at least one salt of at least one metal [A¹] and/or [A²]optionally dissolved in a suitable solvent;(b) adding at least one source of at least one non-metal [B¹] and/or[B²] to obtain an intermediate compound [A¹B¹]/[A²B²];(c) coating said intermediate compound [A¹B¹]/[A²B²] from step (b),optionally in the presence of a solvent, by bringing it into contactwith a source of a metal phosphonate acid and/or derivatives thereof,wherein the metal phosphonate follows one of the following structuresaccording to formula (I), (II), (III), (IV) and/or (V)

and optionally(d) subjecting said coated intermediate of step (c) to illumination withlight with a peak light wavelength of about 300 to about 650 nm toincrease quantum yield of the nano-sized material.

It should be noted that said ligands can be added to crude material,which means that they are incorporated into the last step of the QDsynthesis, but is also possible to use commercial QDs forafter-treatment. The materials may have any possible shape, such as forexample rods, dots, octahedrals, wires, tetrapods, platelets and thelike.

Metal Phosphonates and Derivatives Thereof

“Phosphonate acids” are organophosphorus compounds containing C—PO(OH)2or C—PO(OR)2 groups. Phosphonate acids, typically handled as salts, aregenerally non-volatile solids that are poorly soluble in organicsolvents, but soluble in water and common alcohols.

Phosphonate acids can be alkylated under “Mannich conditions” to giveamino methylated phosphonates, which are useful as complexants. Oneexample is the industrial preparation of nitrilotris (methylenephosphonic acid):

H3+3H3PO3+3CH2O→N(CH2PO3H2)3+3H2O

Phosphonate acids also can be alkylated with acrylic acid derivatives toafford carboxyl functionalized phosphonate acids. This reaction is avariant of the Michael addition:

CH2═CHCO2R+3H3PO3→(HO)2P(O)CH2CH2CO2R

For example, phosphonate esters are prepared using the“Michaelis-Arbuzov reaction”. For example, methyl iodide catalyses theconversion of trimethylphosphite to the phosphonate ester dimethylmethylphosphonate:

P(OMe)3→MePO(OMe)2

In the “Michaelis-Becker reaction”, a hydrogen phosphonate diester isfirst deprotonated and the resulting anion is alkylated.

These preparation examples are intended only to give an indication ofhow the phosphonates according to the invention can be manufactured. Theabove cited examples therefore are not limiting examples according tothe present invention. Other methods of manufacture are well known tothe person skilled in the art and are described in the literature.

Preferably said metal phosphonates follow formula (I), (II), (III), (IV)and/or (V)

wherein R is selected from the group consisting of alkyl, alkenyl,alkynyl, aryl and alkylaryl and wherein R comprises at least 2 and notmore than 20 carbon atoms, and wherein X is selected from the groupconsisting of hydroxyl, ester and ether.

In some embodiments of the present invention R further comprises atleast one functional group selected from the group consisting ofhydroxyl, carbonyl, carboxyl, ether, ester, amino, thio, silyl, sulfoand halogen. Preferably said metal phosphonates follow formula (I)and/or (II).

The metal cation used for the metal phosphonate is selected from thegroup consisting of: Mg, Ca, Ba, Cu, Fe, Zn or their mixtures.Preferably the metal cation used for the metal phosphonate is Mg and/orZn. In the most preferred embodiment the metal cation used for the metalphosphonate is Zn.

The preferred ligands may have the general structures (structure I, II,III, IV and V):

Commonly used suitable metal phosphonates include, but are not limitedto Zn-Octadecylphosphonate, Zn-Hexadecylphosphoanate,Zn-Tetradecylphosphoanate, Zn-tetraethyl methylenediphosphonate, andmixtures thereof.

In some embodiments the phosphonate group of formula (I), (II), (III),(IV) and/or (V) can be replaced by a phosphate group derivative.

It should be noted that the presence of a bivalent metal, as metalcation, in particular zinc, is crucial for the invention. Note that inthe absence of such metals phosphonates exhibit rather low quantumyields.

The preferred ligands represent Zn-phosphonates and/or derivativesthereof, representing so-called Z-type ligands as defined in NATUREMATERIALS 15, pp 141-153 (2016).

Semiconductor Materials

Suitable semiconductor materials forming the core or the core/shell bodyof the material according to the present invention may represent singlecompounds or mixtures of two, three or even more of them.

In a first preferred embodiment of the present invention said core isformed from one, two or more compounds according to formula (VI)

[A ¹ B ¹]  (VI)

in which[A¹] stands for a metal selected from the group consisting of zinc,cadmium, indium or their mixtures;[B¹] stands for a non-metal selected form the group consisting ofsulphur, selenium, phosphor or their mixtures.

More preferably [A¹B¹] stands for one, two or more compounds selectedfrom the group consisting of CdS, CdSe, CdSeS, CdZnS, ZnS, ZnSe, ZnSeS,and InP.

In a most preferred embodiment of the present invention

[A¹] stands for indium; and[B¹] stands for phosphor.

According to the present invention, a type of shape of the core of thesemiconducting light emitting nanoparticle, and shape of thesemiconducting light emitting nanoparticle to be synthesized are notparticularly limited.

For examples, spherical shaped, elongated shaped, star shaped,polyhedron shaped, pyramidal shaped, tetrapod shaped, tetrahedronshaped, platelet shaped, cone shaped, and irregular shaped core and-or asemiconducting light emitting nanoparticle can be synthesized.

In some embodiments of the present invention, the average diameter ofthe core is in the range from 1.5 nm to 3.5 nm.

In another preferred embodiment of the present invention said shell orsaid shells are formed from one, two or more compounds according toformula (VII),

[A ² B ²]  (VII)

in which[A²] stands for a metal selected from the group consisting of zinc,cadmium or their mixtures;[B²] stands for a non-metal selected form the group consisting ofsulphur, selenium, or their mixtures.

Preferably [A²B²] stands for one, two or more compounds selected fromthe group consisting of CdS, CdSe, CdSeS, CdZnS, ZnS, ZnSe, ZnTe,ZnTeSeS and ZnSeS.

In a most preferred embodiment of the present invention

[A²] stands for zinc; and[B²] stands for selenium.

Overall preferred are materials comprise a core shell structure of thecore

[A¹B¹] and at least one shell [A²B²], said core/shell structure[A¹B¹]/[A²B²] being selected from the group consisting of CdSeS/CdZnS,CdSeS,CdS/ZnS, CdSeS/CdS,ZnS CdSe/ZnS, InP/ZnS, InP/ZnSe, InP/ZnSe, ZnS,InP(Zn)/ZnSe, InP(Zn)/ZnSe, ZnS, InP(Zn)/ZnSe,ZnS,ZnTe, ZnSe/CdS,ZnSe/ZnS or their mixtures.

In another preferred embodiment of the present invention the materialsare free of cadmium.

In a most preferred embodiment of the present invention thesemiconductor nano-sized light emitting materials comprise a core [A¹B¹]and at least one shell [A²B²], wherein

[A¹] stands for indium;[B¹] stands for phosphor;[A²] stands for zinc; and[B²] stands for selenium. In some embodiments of the present invention,

the semiconducting light emitting nanoparticle further comprises a 2ndshell layer onto said shell layer, preferably the 2nd shell layercomprises or a consisting of a 3rd element of group 12 of the periodictable and a 4th element of group 16 of the periodic table, morepreferably the 3rd element is Zn, and the 4th element is S, Se, or Tewith the proviso that the 4th element and the 2nd element are not thesame.

In a preferred embodiment of the present invention, the 2nd shell layeris represented by following formula (IX),

ZnSxSeyTez,  (IX)

wherein the formula (IX), 0≤x≤1, 0≤y≤1, 0≤z≤1, and x+y+z=1, preferably,the shell layer is ZnSe, ZnSxSey, ZnSeyTez, or ZnSxTez with the provisothat the shell layer and the 2nd shell layer is not the same.

In some embodiments of the present invention, said 2nd shell layer canbe an alloyed shell layer or a graded shell layer, preferably saidgraded shell layer is ZnSxSey, ZnSeyTez, or ZnSxTez, more preferably itis ZnSxSey. In some embodiments of the present invention, thesemiconducting light emitting nanoparticle can further comprise one ormore additional shell layers onto the 2nd shell layer as a multishell.

According to the present invention, the term “multishells” stands forthe stacked shell layers consisting of three or more shell layers.

For example, CdSe/CdS, CdSeS/CdZnS, CdSeS/CdS/ZnS, ZnSe/CdS, CdSe/ZnS,InP/ZnS, InP/ZnSe, InP/ZnSe/ZnS, InZnP/ZnS, InZnP/ZnSe, InZnP/ZnSe/ZnS,InGaP/ZnS, InGaP/ZnSe, InGaP/ZnSe/ZnS, InZnPS/ZnS, InZnPS ZnSe,InZnPS/ZnSe/ZnS, ZnSe/CdS, ZnSe/ZnS or combination of any of these, canbe used. Preferably, InP/ZnS, InP/ZnSe, InP/ZnSexS1-x,InP/ZnSexS1-x/ZnS, InP/ZnSe/ZnS, InZnP/ZnS, InP/ZnSexTe1-x/ZnS,InP/ZnSexTe1-x, InZnP/ZnSe, InZnP/ZnSe/ZnS, InGaP/ZnS, InGaP/ZnSe,InGaP/ZnSe/ZnS.

Manufacturing Process

Another object of the present invention is directed to a process formanufacturing a semiconductor nano-sized light emitting materialcomprising or consisting of a core, optionally one or more shell layersand metal phosphonates and/or derivatives thereof coated onto the coreor the outermost surface of the shell layers, comprising or consistingof the following steps:

(a) providing at least one salt of at least one metal [A¹] and/or [A²]optionally dissolved in a suitable solvent;(b) adding at least one source of at least one non-metal [B¹] and/or[B²] to obtain an intermediate compound [A¹B¹] or [A¹B¹]/[A²B²];(c) coating said intermediate compound [A¹B¹]/[A²B²] from step (b),optionally in the presence of a solvent, by bringing it into contactwith a source of metal phosphonates and/or derivatives thereof, andoptionally(d) subjecting said coated intermediate of step (c) to illumination withlight with a peak light wavelength of about 300 to about 650 nm toincrease quantum yield of the nano-sized material.

Therefore, the present invention includes two alternative embodimentsfor the materials: the first is a structure consisting of a [A¹B¹] as asingle core on which the ligand is deposited and the second is astructure consisting of a core [A¹B¹] and at least one shell [A²B²],preferably two or more shells [A²B²]² to [A^(x)B^(x)]^(x). In case thematerials consist of a core and at least one shell, core material [A¹B¹]and [A²B²] are different, for example InP as the core and ZnSe forming ashell. In case there are more shells, the materials may be stilldifferent, such as for example InP/ZnS, ZnSe, however it also possiblethat core and for example the outer shell are identical, e.g. ZnS/ZnSe,ZnS.

Therefore, a preferred embodiment of the present invention is a processwherein step (a) and/or step (b) encompasses providing salts of twodifferent metals [A¹] or [A²] and/or adding sources of two differentnon-metals [B¹] or [B²] respectively. In case all raw materials areadded at the same time a core consisting of all these compounds isformed. However, it is particularly preferred forming the core first andsubsequently adding those components designated to form a shell aroundsaid core. This can be done stepwise to build up complex particles witha core and two or more shells.

For example, suitable salts of metal [A¹] or [A²] encompass halides,particularly chlorides or iodides, or carboxylates, such as for exampleacetates or oleates. Suitable sources of non-metals [B¹] or [B²]comprise for example Tris(trimethylsilyl)phosphine. The molar ratio ofthese components [A] and [B] can differ in wide ranges, however it ispreferred to apply molar ratios in the range of about 5:1 to 1:5,preferably about 2:1 to 1:2 and particularly about 1:1.

Reaction usually takes place in the presence of a solvent, for example ahigh-boiling amine like oleyl amine. Once the components to form thecore are brought into contact they were kept under reflux at atemperature of about 150 to about 250° C. Subsequently the remainingcomponents designated to form the shell are introduced an temperatureincreased stepwise up to 350° C., preferably 200 to 320° C. The completereaction requires up to 5 hours.

Once reaction is completed the intermediate semiconductor material[AB]—either consisting of a single core or showing a core-shell(s)structure—is purified by washing and centrifugation using polar andnon-polar solvents. Subsequently the nanocrystals are dissolved or atleast dispersed in an organic solvent (e.g. toluene) and treated with asolution of a metal phosphonate and/or derivatives thereof as defined indetail above.

The metal phosphonates and/or derivatives thereof are deposited on thesurface of the intermediate compound [A¹B¹] or [A¹B¹]/[A²B²] in anamount of from about 2 to about 98 wt. %, based on the total solidcontent of the sample, which is the weight of QD and ligand, morepreferably from about 3 to about 50 wt. % and even more preferably fromabout 5 to about 25 wt. %, which may depend on the molar mass of theligand.

A critical step for producing the new materials is illumination usingblue light. Preferred peak light wavelengths range from about 300 toabout 650 nm and particularly from about 365 about 470 nm. In anotherpreferred embodiment light intensities range from about 0.025 to about 1Wcm⁻², more preferably from about 0.05 to about 0.5 Wcm⁻².

Preferred Embodiments

A preferred embodiment of the present invention is a metal phosphonatewhich follows formula (I), (II), (III), (IV) and/or (V), preferably saidat least one metal phosphonate follows formula (I) and/or (II).

wherein R is selected from the group consisting of alkyl, alkenyl,alkynyl, aryl and alkylaryl and wherein R comprises at least 2 and notmore than 20 carbon atoms, and wherein X is selected from the groupconsisting of hydroxyl, ester and ether; and wherein the metal cation isZn.

In a further preferred embodiment of the present invention the metalcation used for the metal phosphonate is Zn and the semiconductornano-sized light emitting materials comprise a core [A¹B¹] and at leastone shell [A²B²], wherein

[A¹] stands for indium;[B¹] stands for phosphor;[A²] stands for zinc; and[B²] stands for selenium.

Matrix Composition

Another object of the present invention refers to a compositioncomprising at least one semiconductor nano-sized light emitting materialas explained above and at least one additional material, preferably theadditional material is selected from the group consisting of organiclight emitting materials, inorganic light emitting materials, chargetransporting materials, scattering particles, and matrix materials,preferably the matrix materials are optically transparent polymers.Preferably the matrix materials are optically transparent polymers.

According to the present invention, a wide variety of publically knownmatrix materials suitable for optical devices can be used preferably. Ina preferred embodiment according to the invention the matrix materialused is transparent.

According to the present invention, the term “transparent” means atleast around 60% of incident light transmit at the thickness used in anoptical medium and at a wavelength or a range of wavelength used duringoperation of an optical medium. Preferably, it is over 70%, morepreferably, over 75%, the most preferably, it is over 80%.

In a preferred embodiment of the present invention, as said matrixmaterial, any type of publically known transparent matrix material,described in for example, WO 2016/134820A can be used.

In some embodiments of the present invention, the transparent matrixmaterial can be a transparent polymer.

According to the present invention the term “polymer” means a materialhaving a repeating unit and having the weight average molecular weight(Mw) 1000 or more. The molecular weight Mw is determined by means of GPC(=gel permeation chromatography) against an internal polystyrenestandard.

In some embodiments of the present invention, the glass transitiontemperature (Tg) of the transparent polymer is 70° C. or more and 250°C. or less.

Tg can be measured based on changes in the heat capacity observed inDifferential scanning colorimetry like described inhttp://pslc.ws/macrog/dsc.htm, Rickey J Seyler, Assignment of the GlassTransition, ASTM publication code number (PCN) 04-012490-50.

For examples, as the transparent polymer for the transparent matrixmaterial, poly(meth)acrylates, epoxides, polyurethanes, polysiloxanes,can be used preferably.

In a preferred embodiment of the present invention, the weight averagemolecular weight (Mw) of the polymer as the transparent matrix materialis in the range from 1,000 to 300,000. More preferably it is from 10,000to 250,000.

Solvent Formulation

Another object of the present invention covers a formulation comprisingone or more of the semiconductor nano-sized material or the compositionas explained above and at least one solvent. These kinds of formulationsare of interest in case the material is designated for coating on aspecific surface.

Suitable solvents can be selected from the group consisting of purifiedwater; ethylene glycol monoalkyl ethers, such as, ethylene glycolmonomethyl ether, ethylene glycol monoethyl ether, ethylene glycolmonopropyl ether, and ethylene glycol monobutyl ether; diethylene glycoldialkyl ethers, such as, diethylene glycol dimethyl ether, diethyleneglycol diethyl ether, diethylene glycol dipropyl ether, and diethyleneglycol dibutyl ether; ethylene glycol alkyl ether acetates, such as,methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycolalkyl ether acetates, such as, propylene glycol monomethyl ether acetate(PGMEA), propylene glycol monoethyl ether acetate, and propylene glycolmonopropyl ether acetate; ketones, such as, methyl ethyl ketone,acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone;alcohols, such as, ethanol, propanol, butanol, hexanol, cyclo hexanol,ethylene glycol, and glycerin; esters, such as, ethyl3-ethoxypropionate, methyl 3-methoxypropionate and ethyl lactate; andcyclic asters, such as, γ-butyro-lactone; chlorinated hydrocarbons, suchas chloroform, dichloromethane, chlorobenzene, dichlorobenzene.

Also preferred are solvents selected from one or more members of thegroup consisting of aromatic, halogenated and aliphatic hydrocarbonssolvents, more preferably selected from one or more members of the groupconsisting of toluene, xylene, ethers, tetrahydrofuran, chloroform,dichloromethane and heptane.

Those solvents are used singly or in combination of two or more, and theamount thereof depends on the coating method and the thickness of thecoating.

More preferably, propylene glycol alkyl ether acetates, such as,propylene glycol monomethyl ether acetate (hereafter “PGMEA”), propyleneglycol monoethyl ether acetate, propylene glycol monopropyl etheracetate, purified water or alcohols can be used.

Even more preferably, purified water can be used.

The amount of the solvent in the formulation can be freely controlledaccording to further treatments. For example, if the formulation isdesignated to be spray-coated, it can contain the solvent in an amountof 90 wt. % or more. Further, if a slit-coating method, which is oftenadopted in coating a large substrate, is to be carried out, the contentof the solvent is normally 60 wt. % or more, preferably 70 wt. % ormore.

Devices

The present invention is also directed to the use of the semiconductornano-sized light emitting material of the present invention in anelectronic device, optical device or in a biomedical device as forexample In some embodiments of the present invention, the optical devicecan be a liquid crystal display, Organic Light Emitting Diode (OLED),backlight unit for display, Light Emitting Diode (LED), Micro ElectroMechanical Systems (here in after “MEMS”), electro wetting display, oran electrophoretic display, a lighting device, and/or a solar cell.

The present invention also covers an optical medium comprising thesemiconductor nano-sized light emitting material, the composition or theformulation each of them as explained above.

Finally, the present invention also refers to an optical devicecomprising said optical medium as explained above.

Further Embodiments

Embodiment 1: A semiconductor nano-sized light emitting materialcomprising or consisting of a core, optionally one or more shell layersand a ligand coated onto the core or the outermost surface of the shelllayers, wherein the ligand is one or more metal phosphonate and/orderivatives thereof, and wherein the metal phosphonate follows one ofthe following structures according to formula (I), (II), (III), (IV)and/or (V)

wherein R is selected from the group consisting of alkyl, alkenyl,alkynyl, aryl and alkylaryl and wherein R comprises at least 2 and notmore than 20 carbon atoms, and

wherein X is selected from the group consisting of hydroxyl, ester andether.

Embodiment 2: The semiconductor nano-sized light emitting materialaccording to embodiment 1, wherein the metal phosphonate follows one ofthe following structures according to formula (I), (II), (III), (IV)and/or (V), and wherein R further comprises at least one functionalgroup selected from the group consisting of hydroxyl, carbonyl,carboxyl, ether, ester, amino, thio, silyl, sulfo and halogen.

Embodiment 3: The semiconductor nano-sized light emitting materialaccording to embodiment 1 or 2, wherein the metal cation used for themetal phosphonate is selected from the group consisting of: Mg, Ca, Ba,Cu, Fe, Zn or their mixtures.

Embodiment 4: The semiconductor nano-sized light emitting materialaccording to any of embodiments 1 to 3, wherein the metal cation usedfor the metal phosphonate is Mg and/or Zn.

Embodiment 5: The semiconductor nano-sized light emitting materialaccording to any of embodiments 1 to 4, wherein the metal cation usedfor the metal phosphonate is Zn.

Embodiment 6: The semiconductor nano-sized light emitting materialaccording to any of embodiments 1 to 5, wherein said semiconductornano-sized light emitting material comprises or consists of a core andoptionally one or more shell layers wherein said core is formed fromone, two or more compounds according to formula (VI),

[A ¹ B ¹]  (VI)

in which

[A¹] stands for a metal selected from the group consisting of zinc,cadmium, indium or their mixtures;

[B¹] stands for a non-metal selected form the group consisting ofsulphur, selenium, phosphor or their mixtures.

Embodiment 7: The semiconductor nano-sized light emitting material ofembodiment 6, wherein [A¹B¹] stands for one, two or more compoundsselected from the group consisting of CdS, CdSe, CdSeS, CdZnS, ZnS,ZnSe, ZnSeS, and InP.

Embodiment 8: The semiconductor nano-sized light emitting materialaccording to embodiment 6, wherein

[A¹] stands for indium; and

[B¹] stands for phosphor.

Embodiment 9: The semiconductor nano-sized light emitting materialaccording to any of embodiments 1 to 7, wherein said shell of saidsemiconductor nano-sized light emitting material is formed from one, twoor more compounds according to formula (VII)

[A ² B ²]  (VII)

in which

[A²] stands for a metal selected from the group consisting of zinc,cadmium or their mixtures;

[B²] stands for a non-metal selected form the group consisting ofsulphur, selenium, or their mixtures.

Embodiment 10: The semiconductor nano-sized light emitting materialaccording to embodiment 9, wherein [A²B²] stands for one, two or morecompounds selected from the group consisting of CdS, CdSe, CdSeS, CdZnS,ZnS, ZnSe and ZnSeS, ZnSeSTe.

Embodiment 11: The semiconductor nano-sized light emitting material ofembodiment 10, wherein said semiconductor nano-sized light emittingmaterial comprises a core shell structure of the core [A¹B¹] and atleast one shell [A²B²], said core/shell structure [A¹B¹]/[A²B²] beingselected from the group consisting of CdSeS/CdZnS, CdSeS,CdS/ZnS,CdSeS/CdS,ZnS CdSe/ZnS, InP/ZnS, InP/ZnSe, InP/ZnSe,ZnS, InP(Zn)/ZnSe,InP(Zn)/ZnSe,ZnS, InP(Zn)/ZnSe,ZnS,ZnTe, ZnSe/CdS, ZnSe/ZnS or theirmixtures.

Embodiment 12: A process for manufacturing a semiconductor nano-sizedlight emitting material comprising or consisting of a core, optionallyone or more shell layers and metal phosphonate acid and/or derivativesthereof coated onto the core or the outermost surface of the shelllayers, comprising or consisting of the following steps:

(a) providing at least one salt of at least one metal [A¹] and/or [A²]optionally dissolved in a suitable solvent;(b) adding at least one source of at least one non-metal [B¹] and/or[B²] to obtain an intermediate compound [A¹B¹] or [A¹B¹]/[A²B²];(c) coating said intermediate compound [A¹B¹]/[A²B²] from step (b),optionally in the presence of a solvent, by bringing it into contactwith a source of metal phosphonate and/or derivatives thereof, andoptionally(d) subjecting said coated intermediate of step (c) to illumination withlight with a peak light wavelength of about 300 to about 650 nm toincrease quantum yield of the nano-sized material.

Embodiment 13: The process of embodiment 12, wherein illumination iscarried out using light with a peak light wavelength of about 365 toabout 470 nm and/or intensities of about 0.025 to about 1 Wcm⁻².

Embodiment 14: A semiconductor nano-sized light emitting materialcomprising or consisting of a core, optionally one or more shell layersand a ligand coated onto the core or the outermost surface of the shelllayers, obtainable or obtained by the following steps:

(a) providing at least one salt of at least one metal [A¹] and/or [A²]optionally dissolved in a suitable solvent;(b) adding at least one source of at least one non-metal [B¹] and/or[B²] to obtain an intermediate compound [A¹B¹]/[A²B²];(c) coating said intermediate compound [A¹B¹]/[A²B²] from step (b),optionally in the presence of a solvent, by bringing it into contactwith a source of a metal phosphonate and/or derivatives thereof whereinthe metal phosphonate follows one of the following structures accordingto formula (I), (II), (III), (IV) and/or (V)

and optionally(d) subjecting said coated intermediate of step (c) to illumination withlight with a peak light wavelength of about 300 to about 650 nm toincrease quantum yield of the nano-sized material.

Embodiment 15: A composition comprising at least one semiconductornano-sized light emitting material according to any one of embodiments 1to 11, 14, and at least one additional matrix material.

Embodiment 16: A formulation comprising one or more of the semiconductornano-sized material according to any one of embodiments 1 to 11, 14, orthe composition in embodiment 15, and at least one solvent.

Embodiment 17: The use of the semiconductor nano-sized light emittingmaterial according to any one of embodiments 1 to 11, 14, or thecomposition in embodiment 15 or the formulation of embodiment 16, in anelectronic device, optical device or in a biomedical device.

Embodiment 18: An optical medium comprising the semiconductor nano-sizedlight emitting according to any one of embodiments 1 to 11, 14, or thecomposition in embodiment 15 or the formulation of embodiment 16.

Embodiment 19: An optical device comprising said optical mediumaccording to embodiment 18.

EXAMPLES

Several semiconductors are prepared and subjected to surface treatment.Subsequently they are irradiated to measure quantum yields.

For illumination, a lighting setup built with Philips Fortimo 3000 lm34W 4000K LED downlight module (phosphor disc removed). A 1.9 nm thickPerspex Pane® is placed on its top. The distance between the LEDs andthe Perspex Pane® is 31.2 mm. The 20 ml sealed sample vials are placedon the Perspex Pane® inside a plastic cylinder (diameter 68 mm, height100 mm). A photo enhancement system with sealed sample vials inside thecylinder is used.

The vials with the solution of QDs are placed on the Perspex andilluminated from below. Optionally, to prevent the solution fromextensive heating and evaporation of the solvent, the vials are placedin the water bath. The peak wavelength of the illumination is 455 nm.The irradiance at 450 nm is measured by an Ophir Nova II® and PD300-UVphotodetector and measured to be 300 mW/cm².

Example 1 Synthesis of InP/ZnSe

112 mg of InI₃, and 150 mg ZnCl₂ are dissolved in 2.5 mL oleylamine. At180° C. 0.22 mL of hexaethylphosphorous triamide (DEA)₃P) is added tothe solution and is kept at this temperature for 20 min. After 20 min,0.55 mL of anion shell precursor (2M TOP:Se) is added slowly in thesolution. The solution is then heated stepwise, followed by successiveinjections of cation (2.4 mL of 0.4M Zn-acetate in oleylamine) and anion(0.38 mL of 2M TOP:Se) shell precursor at temperatures between 200° C.and 320° C.

Example 2 Synthesis and Purification of Zn-ODPA Precursor

33 mg (1.5 mmol) of zinc acetate dehydrate (Zn(Ac)2) (99.99% purity, CAS#557-34-6, 383317-100G Sigma-Aldrich), 1.25 gr (3.75 mmol) ofoctadecylphosphonic acid (ODPA) (˜90% purity, PCI, Lot #350001N11-B, 250gr) and 3 gr of 1-Octadecene (ODE) (90% purity, CAS #112-88-9, 0806-1LSigma-Aldrich) are added in to flask of 50 ml.

The continuously stirred mixture is degassed at 130° C. for 2 hours.Then Argon is inserted, and temperature is increased up to 330° C. Thesolution becomes clear at ˜280° C. Further, the solution is continuouslystirred and heated at 330° C. for 30 minutes.

Afterwards the solution, i.e. Zn-ODPA in ODE is cooled to roomtemperature. In order to clean raw Zn-ODPA precursor from ODE and fromunreacted zinc acetate, ethyl acetate is used. Samples with cleanedZn-ODPA and pure ODPA are analyzed using Mass-spectra Analysis,Thermogravimetric Analysis and P-NMR.

Compound Content (%) Znx[ODPA]y 66.7 Znx[ODPA ester]y 10.5 UnreactedZinc 16.1 Other contaminations 6.7

Example 3 Zn-ODPA Photo-Deposition+Characterization Method

2 ml of the sample from example 1 is purified from access ligands usingcentrifugation and toluene and ethanol as solvent/anti-solvent. 96 mg ofthe precipitant was dissolved in 1 ml of hexanes or toluene (anhydrous).This solution is placed under blue illumination for 48 hours.

After 48 hours the quantum yields of the sample is measured usingHamamatsu absolute quantum yield spectrometer (model: QuantaurusC11347).

Example 4

60 mg of cleaned and dried Zn-ODPA ligands are dissolved in 4 ml ofanhydrous toluene. Sonication (10 min) and hot water bath (˜70° C.) areapplied to accelerate dissolving Zn-ODPA in toluene. QDs (concentration6.5 mg/ml) from comparative example 1 are combined with the Zn-ODPA andstirred for 72 hours.

This solution is placed under blue illumination for 48 hours. After 48hours the quantum yields of the sample is measured using Hamamatsuabsolute quantum yield spectrometer (model: Quantaurus C11347).

Experimental Results

Table 2 shows the quantum yield (QY) measurement summary for the treatedsamples with and without Zn-ODPA.

TABLE 2 Samples QY (%) Example 3 25% Example 4 60%

It clearly shows that the QY of the QDs treated with Zn-ODPA is 35%higher than the QY of the untreated QDs.

1. A semiconductor nano-sized light emitting material comprising orconsisting of a core, optionally one or more shell layers and a ligandcoated onto the core or the outermost surface of the shell layers,wherein the ligand is one or more metal phosphonate and/or derivativesthereof, and wherein the metal phosphonate follows one of the followingstructures according to formula (I), (II), (III), (IV) and/or (V)

wherein R is selected from the group consisting of alkyl, alkenyl,alkynyl, aryl and alkylaryl and wherein R comprises at least 2 and notmore than 20 carbon atoms, and wherein X is selected from the groupconsisting of hydroxyl, ester and ether.
 2. The material according toclaim 1, wherein the metal phosphonate follows one of the followingstructures according to formula (I), (II), (III), (IV) and/or (V), andwherein R further comprises at least one functional group selected fromthe group consisting of hydroxyl, carbonyl, carboxyl, ether, ester,amino, thio, silyl, sulfo and halogen.
 3. The material according toclaim 1, wherein the metal cation used for the metal phosphonate isselected from the group consisting of: Mg, Ca, Ba, Cu, Fe, Zn or theirmixtures.
 4. The material according to claim 1, wherein the metal cationused for the metal phosphonate is Mg and/or Zn.
 5. The materialaccording to claim 1, wherein the metal cation used for the metalphosphonate is Zn.
 6. The material according to claim 1, wherein saidsemiconductor nano-sized light emitting material comprises or consistsof a core and optionally one or more shell layers wherein said core isformed from one, two or more compounds according to formula (VI),[A ¹ B ¹]  (VI) in which [A¹] stands for a metal selected from the groupconsisting of zinc, cadmium, indium or their mixtures; [B¹] stands for anon-metal selected form the group consisting of sulphur, selenium,phosphor or their mixtures.
 7. The semiconductor nano-sized lightemitting material of claim 6, wherein [A¹B¹] stands for one, two or morecompounds selected from the group consisting of CdS, CdSe, CdSeS, CdZnS,ZnS, ZnSe, ZnSeS, and InP.
 8. The semiconductor nano-sized lightemitting material according to claim 6, wherein [A¹] stands for indium;and [B¹] stands for phosphor.
 9. The material according to claim 1,wherein said shell of said semiconductor nano-sized light emittingmaterial is formed from one, two or more compounds according to formula(VII)[A ² B ²]  (VII) in which [A²] stands for a metal selected from thegroup consisting of zinc, cadmium or their mixtures; [B²] stands for anon-metal selected form the group consisting of sulphur, selenium, ortheir mixtures.
 10. The material according to claim 9, wherein [A²B²]stands for one, two or more compounds selected from the group consistingof CdS, CdSe, CdSeS, CdZnS, ZnS, ZnSe and ZnSeS, ZnSeSTe.
 11. Thematerial of claim 10, wherein said semiconductor nano-sized lightemitting material comprises a core shell structure of the core [A¹B¹]and at least one shell [A²B²], said core/shell structure [A¹B¹]/[A²B²]being selected from the group consisting of CdSeS/CdZnS, CdSeS,CdS/ZnS,CdSeS/CdS,ZnS CdSe/ZnS, InP/ZnS, InP/ZnSe, InP/ZnSe,ZnS, InP(Zn)/ZnSe,InP(Zn)/ZnSe,ZnS, InP(Zn)/ZnSe,ZnS,ZnTe, ZnSe/CdS, ZnSe/ZnS or theirmixtures.
 12. A process for manufacturing a semiconductor nano-sizedlight emitting material comprising or consisting of a core, optionallyone or more shell layers and metal phosphonate acid and/or derivativesthereof coated onto the core or the outermost surface of the shelllayers, comprising or consisting of the following steps: (a) providingat least one salt of at least one metal [A¹] and/or [A²] optionallydissolved in a suitable solvent; (b) adding at least one source of atleast one non-metal [B¹] and/or [B²] to obtain an intermediate compound[A¹B¹] or [A¹B¹]/[A²B²]; (c) coating said intermediate compound[A¹B¹]/[A²B²] from step (b), optionally in the presence of a solvent, bybringing it into contact with a source of metal phosphonate and/orderivatives thereof, and optionally (d) subjecting said coatedintermediate of step (c) to illumination with light with a peak lightwavelength of about 300 to about 650 nm to increase quantum yield of thenano-sized material.
 13. The process of claim 12, wherein illuminationis carried out using light with a peak light wavelength of about 365 toabout 470 nm and/or intensities of about 0.025 to about 1 Wcm⁻².
 14. Asemiconductor nano-sized light emitting material comprising orconsisting of a core, optionally one or more shell layers and a ligandcoated onto the core or the outermost surface of the shell layers,obtainable or obtained by the following steps: (a) providing at leastone salt of at least one metal [A¹] and/or [A²] optionally dissolved ina suitable solvent; (b) adding at least one source of at least onenon-metal [B¹] and/or [B²] to obtain an intermediate compound[A¹B¹]/[A²B²]; (c) coating said intermediate compound [A¹B¹]/[A²B²] fromstep (b), optionally in the presence of a solvent, by bringing it intocontact with a source of a metal phosphonate and/or derivatives thereof,wherein the metal phosphonate follows one of the following structuresaccording to formula (I), (II), (III), (IV) and/or (V)

and optionally (d) subjecting said coated intermediate of step (c) toillumination with light with a peak light wavelength of about 300 toabout 650 nm to increase quantum yield of the nano-sized material.
 15. Acomposition comprising at least one semiconductor nano-sized lightemitting material according to claim 1, and at least one additionalmatrix material.
 16. A formulation comprising one or more of thesemiconductor nano-sized material according to claim 1, and at least onesolvent.
 17. (canceled)
 18. An optical medium comprising in said mediumthe semiconductor nano-sized light emitting material according toclaim
 1. 19. An optical or electronic device comprising said opticalmedium according to claim 18.